[go: up one dir, main page]

WO1998011051A1 - Procede de preparation simultanee de 6-aminocapronitrile et de diamine d'hexamethylene - Google Patents

Procede de preparation simultanee de 6-aminocapronitrile et de diamine d'hexamethylene Download PDF

Info

Publication number
WO1998011051A1
WO1998011051A1 PCT/EP1997/004542 EP9704542W WO9811051A1 WO 1998011051 A1 WO1998011051 A1 WO 1998011051A1 EP 9704542 W EP9704542 W EP 9704542W WO 9811051 A1 WO9811051 A1 WO 9811051A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
phosphorus
adiponitrile
mixture
compound
Prior art date
Application number
PCT/EP1997/004542
Other languages
German (de)
English (en)
Inventor
Guido Voit
Klemens Flick
Hermann Luyken
Alwin Rehfinger
Peter Bassler
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to US09/254,454 priority Critical patent/US6147247A/en
Priority to EP97941948A priority patent/EP0929513B1/fr
Priority to AU43803/97A priority patent/AU4380397A/en
Priority to JP10513186A priority patent/JP2001500135A/ja
Priority to CA002265488A priority patent/CA2265488C/fr
Priority to DE59703361T priority patent/DE59703361D1/de
Priority to BR9711718A priority patent/BR9711718A/pt
Publication of WO1998011051A1 publication Critical patent/WO1998011051A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
    • C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups

Definitions

  • the present invention relates to a process for gleichzeiti ⁇ gen Preparation of 6-aminocapronitrile and hexamethylenediamine starting the and obtain a phosphorus-containing compound and essentially comprises adiponitrile by reaction of butadiene or pentenenitriles with hydrogen cyanide in the presence of a phosphorus-containing compound-containing catalyst from a mixture, has been.
  • adiponitrile by reacting butadiene or pentenenitriles with hydrocyanic acid in the presence of a catalyst containing a phosphorus-containing compound is generally known, for example from: K. Weissermel, H.-J.Arpe, Industrial Organic Chemistry, 3rd edition, VCH publishing company mbH, Weinheim, 1988, pages 263-264, method 3.
  • a disadvantage of the use of adiponitrile, which was obtained by reacting butadiene or pentenenitriles with hydrocyanic acid in the presence of a catalyst containing a phosphorus-containing compound, in the partial hydrogenation mentioned is that the catalyst used for the hydrogenation is a rapid deactivation and poor 6- Aminocapronitrile yields and selectivities shows.
  • adiponitrile from butadiene and hydrocyanic acid can be carried out by one of the known processes, for example by one of the processes described above: K.Weissermel, H.-J.Arpe, Industrial Organic Chemistry, 3rd edition, VCH Verlagsgesellschaft mbH, Weinheim, 1988, pages 263-264, process 3, in general by carrying out the reaction preferably in the liquid phase on catalysts which, as active component, comprise a complex compound of a metal such as nickel with phosphorus-containing ligands such as phosphine or phosphite compounds, for example, [(C 6 H 5 ) 3 PO) 4 Ni.
  • a metal such as nickel
  • phosphorus-containing ligands such as phosphine or phosphite compounds
  • reaction is carried out in several stages, a mixture of isomeric pentenenitriles and methylbutenenitriles being obtained in the first stage, which is then isomerized to predominantly 3- and 4-pentenenitriles.
  • adipodinitrile is formed by renewed addition of hydrocyanic acid in the presence of the catalysts mentioned.
  • the adiponitrile prepared by this process contains at least one phosphorus-containing compound, generally in
  • a phosphorus-containing compound bond as well as in the case of several compounds, the sum of the phosphorus-containing compounds is also referred to as a phosphorus-containing compound.
  • the proportion by weight of the phosphorus-containing compound is then reduced according to the invention, which advantageously gives proportions by weight of phosphorus-containing compound, calculated as phosphorus, based on adiponitrile, of less than 5 ppm, preferably less than 1 ppm.
  • a phosphorus-containing compound in the mixture there are various methods known per se, such as precipitation, preferably extraction, treatment with a base such as sodium hydroxide solution or potassium hydroxide solution, adsorption or Che sorption, in particular on a metal oxide such as calcium oxide or particularly preferably Distillation into consideration.
  • a base such as sodium hydroxide solution or potassium hydroxide solution
  • adsorption or Che sorption in particular on a metal oxide such as calcium oxide or particularly preferably Distillation into consideration.
  • the distillation can advantageously be carried out at pressures of 1 to 100 mbar, preferably 10 to 200 mbar, the adiponitrile usually being obtained as the top product, since the phosphorus-containing compound is essentially less volatile than adiponinitrile.
  • the partial hydrogenation of adiponitrile can be carried out by one of the known processes, for example by one of the processes described above in US Pat. No. 4,601,8,591, US Pat. No. 2,762,835, US Pat -A 4 235 466 or WO 92/21650 by generally carrying out the hydrogenation in the presence of nickel, cobalt, iron or rhodium-containing catalysts.
  • Catalysts as. Supported catalysts or as unsupported catalysts can be used.
  • suitable catalyst supports are aluminum oxide, silicon dioxide, titanium dioxide, magnesium oxide activated carbon and spinels.
  • Raney nickel and Raney cobalt, for example, are suitable as full catalysts.
  • the catalyst load in the range of 0.05 to 10, preferably from 0.1 to 5, kg of adiponitrile / l l ⁇ ata ysator * h.
  • the hydrogenation is generally carried out at temperatures in the range from 20 to 200, preferably from 50 to 150 ° C., and at hydrogen partial pressures from 0.1 to 40, preferably from 0.5 to 30 MPa.
  • the hydrogenation is preferably carried out in the presence of a solvent, in particular ammonia.
  • the amount of ammonia is generally selected in the range from 0.1 to 10, preferably from 0.5 to 3, kg of ammonia / kg of adiponitrile. 5
  • the molar ratio of 6-aminocapronitrile to hexamethylenediamine, and thus the molar ratio of caprolactam to hexamethylenediamine, can be controlled by the adiponitrile conversion selected in each case.
  • Adiponitrile conversions 10 are preferably carried out in the range from 10 to 90%, preferably from 30 to 80%, in order to obtain high 6-aminocapronitrile selectivities.
  • the sum of 6-aminocapronitrile and hexamethylene diamine is 15 95 to 99%, depending on the catalyst and reaction conditions, hexamethyleneimine being the most important by-product in terms of quantity.
  • reaction is carried out in the presence of ammonia and lithium hydroxide, or a lithium
  • the pressure is generally selected in the range from 2 to 12, preferably from 3 to 10, particularly preferably from 4 to 8 MPa.
  • the residence times depend essentially on the desired yield, selectivity and the desired conversion; The residence time is usually chosen so that a maximum yield is achieved, for example in the range from 50 to 275, preferably from 70 to 200, minutes. 0
  • the pressure and temperature ranges are preferably selected so that the reaction can be carried out in the liquid phase.
  • Ammonia is generally used in an amount such that the 5 weight ratio of ammonia to dinitrile is in the range from 9: 1 to 0.1: 1, preferably from 2.3: 1 to 0.25: 1, particularly preferably from 1 , 5: 1 to 0.4: 1.
  • the amount of lithium hydroxide is generally chosen in the range 0 from 0.1 to 20, preferably from 1 to 10,% by weight, based on the amount of catalyst used.
  • Lithium compounds which form lithium hydroxide under the reaction conditions are: lithium metal, alkyl and 5 aryllithium compounds such as n-butyllithium and phenyllithium. The The amount of these compounds is generally chosen so that the aforementioned amount of lithium hydroxide is obtained.
  • the catalysts used are preferably compounds containing nickel, ruthenium, rhodium, iron and cobalt, preferably those of the Raney type, in particular Raney nickel and Raney cobalt.
  • the catalysts can also be used as supported catalysts, with aluminum oxide, silicon dioxide, zinc oxide, activated carbon or titanium dioxide being used as supports. (see Appl. Het. Cat., 1987, pp. 106-122; Catalysis, Vol. 4 (1981) pp. 1-30).
  • Raney nickel is particularly preferred (for example from BASF AG, Degussa and Grace).
  • the nickel, ruthenium, rhodium, iron and cobalt catalysts can be used with metals from groups VIB (Cr, Mo,) and VIII (Fe, Ru, Os, Co (only in the case of nickel), Rh, Ir, Pd, Pt) of the periodic table can be modified. According to previous observations, the use of especially modified Raney nickel catalysts, for example modified with chromium and / or iron, leads to higher aminonitrile selectivities. (For production see DE-A 2 260 978; Bull. Soc. Chem. 13 (1946) p. 208).
  • the amount of catalyst is generally chosen so that the amount of cobalt, ruthenium, rhodium, iron or nickel is in the range from 1 to 50, preferably from 5 to 20,% by weight, based on the amount used of dinitrile.
  • the catalysts can be used as fixed bed catalysts in the bottom or trickle mode or as suspension catalysts.
  • adiponitrile is partially hydrogenated to 6-aminocapronitrile at elevated temperature and pressure in the presence of a solvent and a catalyst using a catalyst which
  • component (a) if a compound based only on ruthenium or rhodium or ruthenium and rhodium or nickel and rhodium is selected as component (a), the promoter (b) can be omitted if desired, and with the further proviso that component (a) is not iron-based when component (b) is aluminum.
  • Preferred catalysts are those in which component (a) has at least one compound based on a metal, selected from the group consisting of nickel, cobalt and iron, in an amount in the range from 10 to 95% by weight, and also ruthenium and / or Contains rhodium in an amount in the range from 0.1 to 5% by weight, based in each case on the sum of components (a) to (c),
  • component (b) at least one promoter based on a metal, selected from the group consisting of silver, copper, manganese, rhenium, lead and phosphorus, in an amount in the range from 0.1 to 5% by weight, based on (a), contains, and
  • component (c) contains at least one compound based on the alkali metals and alkaline earth metals, selected from the group consisting of lithium, sodium, potassium, cesium, magnesium and calcium, in an amount in the range from 0.1 to 5% by weight .
  • Particularly preferred catalysts are:
  • Catalyst A containing 90% by weight of cobalt oxide (CoO), 5% by weight of manganese oxide (Mn 2 0 3 ), 3% by weight of phosphorus pentoxide and 2% by weight of sodium oxide (Na 2 0),
  • Catalyst B containing 20% by weight of cobalt oxide (CoO), 5% by weight of manganese oxide (Mn 2 0 3 ), 0.3% by weight of silver oxide (Ag 2 0), 70% by weight of silicon dioxide (Si0) , 3.5% by weight of aluminum oxide (A1 2 0 3 ), 0.4
  • iron oxide Fe0 3
  • magnesium oxide MgO
  • calcium oxide CaO
  • Catalyst C containing 20% by weight of nickel oxide (NiO), 67.42% by weight of silicon dioxide (Si0 2 ), 3.7% by weight of aluminum oxide (A1 2 0 3 ), 0.8% by weight of iron oxide ( Fe0 3 ), 0.76% by weight magnesium oxide (MgO), 1.92% by weight calcium oxide (CaO), 3.4% by weight sodium oxide (Na 2 0) and
  • catalysts are those which are selected from the same
  • (a) contain a compound based on iron such as iron oxide and
  • the preferred catalysts can be unsupported or supported catalysts.
  • Suitable carrier materials are, for example, porous oxides such as aluminum oxide, silicon dioxide, aluminum silicates, lanthanum oxide, titanium dioxide, zirconium dioxide, magnesium oxide, zinc oxide and zeolites, and activated carbon or mixtures thereof.
  • the preparation is usually carried out by precursors of components (a) together with precursors of promoters (components (b) and, if desired, precursors of trace components (c) in the presence or absence of carrier materials (depending on the type of catalyst desired precipitates, if desired, the catalyst precursor thus obtained is processed into strands or tablets, dried and then calcined.
  • Carried catalysts are generally also obtainable by impregnating the support with a solution of components (a), (b) and, if desired, (c), where the individual components can be added simultaneously or in succession, or by spraying components (a), (b) and, if desired (c), onto the support by methods known per se.
  • Suitable precursors of components (a) are generally readily water-soluble salts of the aforementioned metals, such as nitrates, chlorides, acetates, formates and sulfates, preferably nitrates.
  • Suitable precursors of components (b) are generally readily water-soluble salts or complex salts of the aforementioned metals such as nitrates, chlorides, acetates, formates and sulfates, and in particular hexachloroplatinate, preferably nitrates and hexachloroplatinate.
  • Suitable precursors of components (c) are generally readily water-soluble salts of the aforementioned alkali metals and alkaline earth metals such as hydroxides, carbonates, nitrates, chlorides, acetates, formates and sulfates, preferably hydroxides and carbonates.
  • the precipitation is generally carried out from aqueous solutions, optionally by adding precipitation reagents, by changing the pH or by changing the temperature.
  • the catalyst pre-mass obtained in this way is usually pre-dried at temperatures in the range from 80 to 150, preferably from 80 to 120 ° C.
  • the calcination is usually carried out at temperatures in the range from 150 to 500, preferably from 200 to 450 ° C. in a gas stream from air or nitrogen.
  • the catalyst mass obtained is generally subjected to a reducing atmosphere (“activation”), for example by being at a temperature in the range from 80 to 250, preferably from 80 to 180 ° C. in the case of catalysts based on ruthenium or rhodium as component (a), or in the range from 200 to 500, preferably from 250 to 400 ° C.
  • activation for example by being at a temperature in the range from 80 to 250, preferably from 80 to 180 ° C. in the case of catalysts based on ruthenium or rhodium as component (a), or in the range from 200 to 500, preferably from 250 to 400 ° C.
  • the catalyst loading is preferably 200 l per 1 catalyst.
  • the activation of the catalyst is advantageously carried out directly in the synthesis reactor, since this usually results in an intermediate step which is otherwise required, namely the passivation of the surface at usually temperatures in the range from 20 to 80, preferably from 25 to 35 ° C. by means of oxygen-nitrogen mixture - like air, falls away.
  • the activation of passivated catalysts is then preferably carried out in a synthesis reactor at a temperature in the range from 180 to 500, preferably from 200 to 350 ° C. in a hydrogen-containing atmosphere.
  • the catalysts can be used as fixed bed catalysts in the bottom or trickle mode or as suspension catalysts.
  • temperatures in the range from 40 to 150 preferably from 50 to 100, particularly preferably from 60 to 90 ° C. are usually chosen; the pressure is generally selected in the range from 2 to 30, preferably from 3 to 30, particularly preferably from 4 to 9 MPa.
  • the residence times depend essentially on the desired yield, selectivity and the desired conversion; The residence time is usually chosen so that a maximum yield is achieved, for example in the range from 50 to 275, preferably from 70 to 200, minutes.
  • ammonia, amines, diamines and triamines with 1 to 6 carbon atoms such as trimethylamine, triethylamine, tripropylamine and tributylamine or alcohols, in particular methanol and ethanol, particularly preferably ammonia, are preferably used as solvents.
  • a dinitrile concentration in the range from 10 to 90, preferably from 30 to 80, particularly preferably from 40 to 70,% by weight, based on the sum of dinitrile and solvent.
  • the amount of catalyst is generally chosen so that the amount of catalyst is in the range from 1 to 50, preferably from 5 to 20,% by weight, based on the amount of dinitrile used.
  • the suspension hydrogenation can be carried out batchwise or, preferably continuously, generally in the liquid phase.
  • the partial hydrogenation can also be carried out batchwise or continuously in a fixed bed reactor in trickle or sump mode, a temperature in the range from 20 to 150, preferably from 30 to 90 ° C. and a pressure in the range from 2 usually being used to 40, preferably from 3 to 30 MPa.
  • the partial hydrogenation is preferably carried out in the presence of a solvent, preferably ammonia, amines, diamines and triamines having 1 to 6 carbon atoms, such as trimethylamine, triethylamine, tripropylamine and tributylamine or alcohol, preferably methanol and ethanol, particularly preferably ammonia.
  • a solvent preferably ammonia, amines, diamines and triamines having 1 to 6 carbon atoms, such as trimethylamine, triethylamine, tripropylamine and tributylamine or alcohol, preferably methanol and ethanol, particularly preferably ammonia.
  • the partial hydrogenation can be carried out in a conventional reactor suitable for this purpose (R1 in the drawing).
  • the hydrogenation gives a mixture which contains 6-aminocapronitrile, hexamethylenediamine and adiponitrile.
  • the separation of 6-aminocapronitrile, hexamethylenediamine and a part essentially containing adiponitrile from the mixture can be carried out simultaneously or in succession in a manner known per se, preferably by distillation, for example according to DE-A 195 002 22 or German application 19 548 289.1.
  • the distillation in the first column K1 in the drawing) is carried out in such a way that the mixture comprising essentially 6-aminocapronitrile, hexamethylene diamine, ammonia, adiponitrile and hexamethyleneimine, preferably a mixture comprising essentially from 1 to 70 , preferably from 5 to 40% by weight of 6-aminocapronitrile,
  • Suitable compounds A are substances which are inert under the distillation conditions and have a boiling point in the range from 60 to 250, preferably from 60 to 150 ° C. at a pressure of 18 bar.
  • Examples include: alkanes, cycloalkanes, aromatics, naphthenes, alcohols, ethers, nitriles and amines with the properties mentioned above, in particular Cs-C ⁇ -alkanes and C 2 -C 4 -alkanols, particularly preferably n-pentane, cyclohexane, triethylamine, ethanol, acetonitrile, n-hexane, di-n-propyl ether, isopropanol , n-butylamine, benzene, very particularly preferably ethanol.
  • Compound A is usually added in an amount in the range from 0.1 to 50, preferably from 1 to 10,% by weight, based on the bottoms I.
  • the bottom I containing essentially 6-aminocapronitrile, hexamethylenediamine, adiponitrile, hexamethyleneimine, inert compound (s) A and ammonia, is subjected, the ammonia content being lower than the reactor discharge from Rl, being subjected to a second distillation to obtain a mixture the inert compound (s) A and ammonia as top product and a bottom II, the distillation being carried out at a bottom temperature in the range from 100 to 250, preferably from 140 to 200 ° C., and a pressure in the range from 2 to 15, preferably from 4 to 12 bar, with the proviso that the pressures of the first and second columns (K2 in the drawing) are coordinated with one another in such a way that a top temperature of over 250 ° C. is obtained at a respective bottom temperature 20 ° C. It may also be advantageous to carry out the condensation at the top of the second column at lower temperatures, the top draw, which consists of pure or more concentrated ammonia, being
  • the vapor from the top of the second column is returned to the first column or its condenser with a compressor after increasing the pressure.
  • the bottom II containing essentially 6-aminocapronitrile, hexamethylenediamine, adiponitrile, hexamethyleneimine and inert compound (s) A, is subjected to a distillation in a third column (K3 in the drawing) to give the inert compound (s) A as the top product and a bottom III, the distillation being carried out at a bottom temperature in the range from 50 to 250, preferably from 140 to 200 ° C.
  • hexamethyleneimine and / or hexamethylenediamine is selected as compound B, or, particularly preferably, no further compound B is added.
  • Compound B is preferably fed to column K3 in an amount in the range from 0.01 to 50, preferably from 0.5 to 10,% by weight, based on the bottom II.
  • the bottom III containing essentially 6-amino-capronitrile, hexamethylenediamine, adiponitrile, hexamethyleneimine and, if desired, inert compound (s) B, is subjected to distillation in a fourth column (K4 in the drawing) to obtain an overhead product KP1, essentially containing Hexamethyleneimine, if desired inert compound (s) B and a side draw SA1, essentially containing hexamethylenediamine, the bottom temperature of the column being in the range from 50 to 250 ° C. and the pressure in the range from 0.05 to 1.5 bar, giving a Swamp IV
  • the column is equipped with a dividing wall in the area between the inlet and side outlet (Petlyuk column), so that the hexamethylenediamine obtained is essentially free from hexamethyleneimine and inert compound (s) B and from other low boilers, where
  • top product KP1 and / or HMD from side draw SA1 are fed to the third column as required or, if appropriate, only partially fed to the third column and the rest is discharged.
  • the bottom IV comprising essentially 6-aminocapronitrile and adiponitrile and any high boilers in a fifth column (K5 in the drawing), is subjected to distillation to give 6-aminocapronitrile with a purity of at least 95%, preferably 99 to 99 , 9%, as the top product and a side draw V, consisting essentially of adiponitrile, and a bottom V, which consists of high boilers and small amounts of adiponitrile.
  • the column is equipped with a dividing wall in the region between the inlet and the side outlet, so that the adiponitrile obtained contains lower proportions of high boilers, the distillation at a bottom temperature in the range from 50 to 5 250 ° C. and a pressure in the range of 10 up to 300 mbar.
  • the bottom V of the column K5 containing adiponitrile and 0 higher-boiling compounds, can also be separated by distillation in a further column K6 and adipodinitrile obtained as the top product VI.
  • the part essentially containing adiponitrile is treated which, in the distillative workup described, of the reaction mixture obtained in the hydrogenation of adiponitrile as side draw V from column K5, as top product VI from column K6 or as bottom product of column D5, preferably as side draw V the column D5 accumulates an acid or an acidic ion exchanger.
  • Suitable acids or acidic ion exchangers are primarily substances which can act as proton donors towards primary, secondary and tertiary saturated and unsaturated amines such as enamines. Acids with a pK a value of at most 10, preferably at most 7, are particularly suitable for this.
  • Inorganic acids such as nitric acid, preferably sulfuric acid, in particular as 100% by weight sulfuric acid or as a mixture containing at least 90% by weight, preferably 96% by weight, in particular with water or phosphoric acid
  • organic acids for example, can be used as acids
  • Carboxylic acids such as adipic acid, 2-ethylhexanoic acid, pimelic acid, suberic acid, undecanedioic acid, terephthalic acid, cyclohexane carboxylic acid, for example sulfonic acid such as p-toluenesulfonic acid, benzenesulfonic acid, as acidic ion exchangers, for example Lewatit S100G1, Amberlyst 15, Dowex 50 WX 8, Bay. K 2431, Amberlite IR-120 and mixtures of such acids and acidic ion exchangers can be used.
  • the reaction of the adiponitrile with the acid can take place in the presence of a liquid diluent such as water, the liquid diluent being able to be added to the adiponitrile together with the acid or before or after the acid addition.
  • a liquid diluent such as water
  • the direct treatment of the adiponitrile which has not been freed of higher-boiling compounds, for example the bottom product V of the column K5 if it does not contain any adiponitrile side draw, is also possible. In this case, the consumption of acid or acidic ion exchanger and the amount of residue obtained after the adiponitrile has been separated off increases.
  • the molar ratio of the acid groups to the basic compounds present in the residue should be at least equimolar, preferably above equimolar. Acid additions of 0.01 to 10% by weight, in particular 0.1 to 2% by weight, based on adiponitrile, have proven to be advantageous.
  • the reaction of the adiponitrile with the acid can be carried out in a manner known per se, such as by mixing or by passing the adiponitrile over an ion exchanger fixed bed, advantageously at temperatures of 2 to 250 ° C., in particular 30 to 100 ° C., which results in Response times of 1 second to 30 minutes, especially 1 second to 10 minutes.
  • the adiponitrile can be separated from the mixture in a manner known per se, advantageously by distillation or extraction.
  • the liquid diluent such as water is added when the residue is reacted with the acid
  • the liquid diluent can preferably be separated off by adsorption, in particular by distillation, before the adiponitrile is separated off.
  • reaction products and any excess acid obtained after the acid addition can advantageously be obtained by
  • the adiponitrile obtained by the process according to the invention can again be used for the partial hydrogenation to hexamethylenediamine and 6-aminocapronitrile, avoiding the addition of by-products which prevent the production of hexamethylenediamine and 6-aminocapronitrile according to specifications.
  • the 6-aminocapronitrile can then be processed in a manner known per se to polyamide 6, hexamethylenediamine with adipic acid to form polymide 66, optionally via the intermediate stage caprolactam.
  • Polyamide 6 and polyamide 66 are technically important materials. example 1
  • the catalyst mass obtained had the following composition: 1.2% by weight of Al, 0.74% by weight of Ca, 0.02% by weight of K,
  • the total of the promoters from group b) is 1.32% by weight, the total of the promoters from group c) calculated as oxides is 1.06% by weight.
  • the reactor at 250 bar was mixed with 400 ml / h of ADN, which was prepared from butadiene and hydrocyanic acid and whose P content was reduced to ⁇ 1 ppm by chemical sorption with calcium oxide, 660 ml of NH 3 and 500 Nl / h H 2 supplied.
  • the catalyst mass obtained had the following composition: 1.2% by weight of Al, 0.74% by weight of Ca, 0.02% by weight of K,
  • the total of promoters from group b) is 1.32% by weight, the total of promoters from group c) calculated as oxides is 1.06% by weight.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de préparation simultanée de 6-aminocapronotrile et de diamine d'hexaméthylène à partir d'un mélange contenant un composé comprenant du phosphore et essentiellement de l'adipodinitrile et obtenu par réaction de butadiène avec de l'acide cyanhydrique en présence d'un catalyseur contenant un composé comprenant du phosphore. Ce procédé se caractérise en ce que (1) la proportion en poids d'un composé comprenant du phosphore, calculée en tant que phosphore, est réduite dans le mélange et que (2) le mélange obtenu est partiellement hydrogéné en présence d'un catalyseur pour former un alpha, omega-aminonitrile et que (3) le 6-aminocapronitrile et la diamine d'hexaméthylène sont séparés du mélange.
PCT/EP1997/004542 1996-09-10 1997-08-21 Procede de preparation simultanee de 6-aminocapronitrile et de diamine d'hexamethylene WO1998011051A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US09/254,454 US6147247A (en) 1996-09-10 1997-08-21 Process for simultaneously preparing 6-aminocapronitrile and hexamethylene diamine
EP97941948A EP0929513B1 (fr) 1996-09-10 1997-08-21 Procede de preparation simultanee de 6-aminocapronitrile et de diamine d'hexamethylene
AU43803/97A AU4380397A (en) 1996-09-10 1997-08-21 Process for simultaneously preparing 6-aminocapronitrile and hexamethylene diamine
JP10513186A JP2001500135A (ja) 1996-09-10 1997-08-21 ６―アミノカプロニトリルとヘキサメチレンジアミンの同時製造方法
CA002265488A CA2265488C (fr) 1996-09-10 1997-08-21 Procede de preparation simultanee de 6-aminocapronitrile et de diamine d'hexamethylene
DE59703361T DE59703361D1 (de) 1996-09-10 1997-08-21 Verfahren zur gleichzeitigen herstellung von 6-aminocapronitril und hexamethylendiamin
BR9711718A BR9711718A (pt) 1996-09-10 1997-08-21 Processo para a co-produ-Æo de 6-aminocapro-nitrila e hexametileno-diamina

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19636765.4 1996-09-10
DE19636765A DE19636765A1 (de) 1996-09-10 1996-09-10 Verfahren zur gleichzeitigen Herstellung von 6-Aminocapronitril und Hexamethylendiamin

Publications (1)

Publication Number Publication Date
WO1998011051A1 true WO1998011051A1 (fr) 1998-03-19

Family

ID=7805164

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1997/004542 WO1998011051A1 (fr) 1996-09-10 1997-08-21 Procede de preparation simultanee de 6-aminocapronitrile et de diamine d'hexamethylene

Country Status (16)

Country Link
US (1) US6147247A (fr)
EP (1) EP0929513B1 (fr)
JP (1) JP2001500135A (fr)
KR (1) KR100550177B1 (fr)
CN (1) CN1113854C (fr)
AU (1) AU4380397A (fr)
BR (1) BR9711718A (fr)
CA (1) CA2265488C (fr)
CZ (1) CZ81099A3 (fr)
DE (2) DE19636765A1 (fr)
ES (1) ES2156401T3 (fr)
ID (1) ID18456A (fr)
MY (1) MY116967A (fr)
TR (1) TR199900516T2 (fr)
TW (1) TW372953B (fr)
WO (1) WO1998011051A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7880028B2 (en) 2006-07-14 2011-02-01 Invista North America S.A R.L. Process for making 3-pentenenitrile by hydrocyanation of butadiene
US7897801B2 (en) 2003-05-12 2011-03-01 Invista North America S.A R.L. Process for the preparation of dinitriles
US7919646B2 (en) 2006-07-14 2011-04-05 Invista North America S.A R.L. Hydrocyanation of 2-pentenenitrile
US7973174B2 (en) 2005-10-18 2011-07-05 Invista North America S.A.R.L. Process of making 3-aminopentanenitrile
US7977502B2 (en) 2008-01-15 2011-07-12 Invista North America S.A R.L. Process for making and refining 3-pentenenitrile, and for refining 2-methyl-3-butenenitrile
US8088943B2 (en) 2008-01-15 2012-01-03 Invista North America S.A R.L. Hydrocyanation of pentenenitriles
US8101790B2 (en) 2007-06-13 2012-01-24 Invista North America S.A.R.L. Process for improving adiponitrile quality
US8178711B2 (en) 2006-03-17 2012-05-15 Invista North America S.A R.L. Method for the purification of triorganophosphites by treatment with a basic additive
US8247621B2 (en) 2008-10-14 2012-08-21 Invista North America S.A.R.L. Process for making 2-secondary-alkyl-4,5-di-(normal-alkyl)phenols
US8338636B2 (en) 2009-08-07 2012-12-25 Invista North America S.A R.L. Hydrogenation and esterification to form diesters
US8373001B2 (en) 2003-02-10 2013-02-12 Invista North America S.A R.L. Method of producing dinitrile compounds

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19704615A1 (de) * 1997-02-07 1998-08-13 Basf Ag Verfahren zur Hydrierung von Verbindungen aus der Gruppe der Imine oder Enamine
DE19742221A1 (de) * 1997-09-24 1999-03-25 Basf Ag Verfahren zur Herstellung von aliphatischen alpha,omega-Aminonitrilen
US6346641B1 (en) * 1998-07-20 2002-02-12 Basf Aktiengesellschaft Method for simultaneous production of 6-aminocapronitrile and hexamethylenediamine
DE19839338A1 (de) 1998-08-28 2000-03-02 Basf Ag Verbessertes Verfahren zur gleizeitigen Herstellung von 6-Aminocapronitril und Hexamethylendiamin
WO2009075692A2 (fr) 2007-05-14 2009-06-18 Invista Technologies S.A.R.L. Réacteur et procédé à haut rendement
CN108779060B (zh) * 2016-02-16 2022-01-28 英威达纺织（英国）有限公司 用于选择性腈加氢的促进剂
CN108084035A (zh) * 2017-12-11 2018-05-29 大连理工大学 一种无碱条件下己二腈直接氢化制己二胺的方法
CN114192170A (zh) * 2021-12-27 2022-03-18 于向真 一种从环己酮肟或己内酰胺合成6－氨基己腈的催化剂及其制备方法
CN117000290A (zh) * 2022-04-29 2023-11-07 中国石油化工股份有限公司 六亚甲基亚胺合成己二胺的催化剂及其制备方法和合成己二胺的方法
CN117003648B (zh) * 2022-04-29 2025-08-12 中国石油化工股份有限公司 一种由己内酰胺制备己二胺的方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0077911A1 (fr) * 1981-10-26 1983-05-04 Allied Corporation Hydrogénation sélective de dinitriles en oméga-aminonitriles
GB2212155A (en) * 1987-11-10 1989-07-19 Ici Plc Purification of nitriles
WO1993012073A1 (fr) * 1991-12-18 1993-06-24 Dsm N.V. Procede de preparation d'un aminonitrile par l'hydrogenation partielle d'un compose de nitrile a l'aide d'au moins deux groupes nitriles
DE4235466A1 (de) * 1992-10-21 1994-04-28 Bayer Ag Verfahren zur Herstellung von (cyclo)aliphatischen Aminonitrilen
DE19500222A1 (de) * 1995-01-05 1996-07-11 Basf Ag Verfahren zur gleichzeitigen Herstellung von Caprolactam und Hexamethylendiamin
WO1996023802A1 (fr) * 1995-01-31 1996-08-08 E.I. Du Pont De Nemours And Company Procede de preparation de catalyseurs d'hydrogenation au ruthenium et produits servant a cet effet
DE19548289A1 (de) * 1995-12-22 1997-06-26 Basf Ag Verfahren zur gleichzeitigen Herstellung von Caprolactam und Hexamethylendiamin

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE235466C (fr) *
US2208598A (en) * 1938-09-24 1940-07-23 Du Pont Aliphatic amino-nitriles and process of producing them
DE848654C (de) * 1950-08-19 1952-09-08 Basf Ag Verfahren zur Herstellung von partiellen Hydrierungsprodukten des Adipinsaeuredinitrils
US2762835A (en) * 1953-03-12 1956-09-11 Celanese Corp Preparation of amino nitriles
DE954161C (de) * 1953-09-06 1956-12-13 Siemens Ag Einrichtung an Fernschreibmaschinen mit Tastaturwahl
BE792649A (fr) * 1971-12-13 1973-06-12 Rhone Poulenc Sa Catalyseur a base de nickel raney au fer
US4601859A (en) * 1984-05-04 1986-07-22 Allied Corporation Selective hydrogenation of aliphatic dinitriles to omega-aminonitriles in ammonia with supported, finely dispersed rhodium-containing catalyst
US5151543A (en) * 1991-05-31 1992-09-29 E. I. Du Pont De Nemours And Company Selective low pressure hydrogenation of a dinitrile to an aminonitrile
US5717090A (en) * 1995-01-05 1998-02-10 Basf Aktiengesellschaft Simultaneous preparation of caprolactam and hexamethylenediamine

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0077911A1 (fr) * 1981-10-26 1983-05-04 Allied Corporation Hydrogénation sélective de dinitriles en oméga-aminonitriles
GB2212155A (en) * 1987-11-10 1989-07-19 Ici Plc Purification of nitriles
WO1993012073A1 (fr) * 1991-12-18 1993-06-24 Dsm N.V. Procede de preparation d'un aminonitrile par l'hydrogenation partielle d'un compose de nitrile a l'aide d'au moins deux groupes nitriles
DE4235466A1 (de) * 1992-10-21 1994-04-28 Bayer Ag Verfahren zur Herstellung von (cyclo)aliphatischen Aminonitrilen
DE19500222A1 (de) * 1995-01-05 1996-07-11 Basf Ag Verfahren zur gleichzeitigen Herstellung von Caprolactam und Hexamethylendiamin
WO1996023802A1 (fr) * 1995-01-31 1996-08-08 E.I. Du Pont De Nemours And Company Procede de preparation de catalyseurs d'hydrogenation au ruthenium et produits servant a cet effet
DE19548289A1 (de) * 1995-12-22 1997-06-26 Basf Ag Verfahren zur gleichzeitigen Herstellung von Caprolactam und Hexamethylendiamin

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8373001B2 (en) 2003-02-10 2013-02-12 Invista North America S.A R.L. Method of producing dinitrile compounds
US7897801B2 (en) 2003-05-12 2011-03-01 Invista North America S.A R.L. Process for the preparation of dinitriles
US7973174B2 (en) 2005-10-18 2011-07-05 Invista North America S.A.R.L. Process of making 3-aminopentanenitrile
US8178711B2 (en) 2006-03-17 2012-05-15 Invista North America S.A R.L. Method for the purification of triorganophosphites by treatment with a basic additive
US7880028B2 (en) 2006-07-14 2011-02-01 Invista North America S.A R.L. Process for making 3-pentenenitrile by hydrocyanation of butadiene
US7919646B2 (en) 2006-07-14 2011-04-05 Invista North America S.A R.L. Hydrocyanation of 2-pentenenitrile
US8394981B2 (en) 2006-07-14 2013-03-12 Invista North America S.A R.L. Hydrocyanation of 2-pentenenitrile
US8101790B2 (en) 2007-06-13 2012-01-24 Invista North America S.A.R.L. Process for improving adiponitrile quality
US7977502B2 (en) 2008-01-15 2011-07-12 Invista North America S.A R.L. Process for making and refining 3-pentenenitrile, and for refining 2-methyl-3-butenenitrile
US8088943B2 (en) 2008-01-15 2012-01-03 Invista North America S.A R.L. Hydrocyanation of pentenenitriles
US8247621B2 (en) 2008-10-14 2012-08-21 Invista North America S.A.R.L. Process for making 2-secondary-alkyl-4,5-di-(normal-alkyl)phenols
US8338636B2 (en) 2009-08-07 2012-12-25 Invista North America S.A R.L. Hydrogenation and esterification to form diesters

Also Published As

Publication number Publication date
EP0929513A1 (fr) 1999-07-21
CN1236355A (zh) 1999-11-24
TW372953B (en) 1999-11-01
DE19636765A1 (de) 1998-03-12
DE59703361D1 (de) 2001-05-17
CZ81099A3 (cs) 1999-06-16
JP2001500135A (ja) 2001-01-09
EP0929513B1 (fr) 2001-04-11
ES2156401T3 (es) 2001-06-16
BR9711718A (pt) 1999-08-24
KR100550177B1 (ko) 2006-02-10
TR199900516T2 (xx) 1999-07-21
CA2265488C (fr) 2005-10-25
ID18456A (id) 1998-04-09
MY116967A (en) 2004-04-30
AU4380397A (en) 1998-04-02
CN1113854C (zh) 2003-07-09
CA2265488A1 (fr) 1998-03-19
US6147247A (en) 2000-11-14
KR20000035988A (ko) 2000-06-26

Similar Documents

Publication Publication Date Title
EP0929513B1 (fr) Procede de preparation simultanee de 6-aminocapronitrile et de diamine d'hexamethylene
EP1107941B1 (fr) Procede ameliore de preparation simultanee de 6-aminocapronitrile et de diamine d'hexamethylene
EP1071653B1 (fr) Catalyseur a base de fer pour l'hydrogenation de dinitriles alpha,omega
EP2132162B1 (fr) Procédé de préparation d'éthylène amines
EP0800508B1 (fr) Procede de preparation d'aminonitriles-alpha,omega aliphatiques
EP0927157B1 (fr) Procede de production simultanee de 6-aminocapronitrile et de diamine d'hexamethylene
WO2008104578A1 (fr) Procédé de fabrication d'éthylénamines à partir d'aan brut
EP2961731B1 (fr) Procédé de production d'éthylène diamine en utilisant de l'acide prussique dépourvu de so2
EP1868988B1 (fr) Procede de production de nitriles satures
EP0931058B1 (fr) Catalyseurs convenant a la preparation d'alpha, omega-aminonitriles aliphatiques par hydrogenation partielle de dinitriles aliphatiques
EP0925276B1 (fr) Procede pour la preparation d'alpha-omega-aminonitriles aliphatiques
EP0771784A1 (fr) Procédé pour la préparation de l'aminométhyl-3-triméthyl-3,5,5-cyclohexylamine
EP1098869B1 (fr) Procede perfectionne pour la preparation simultanee de 6-aminocapronitrile et d'hexamethylenediamine
EP1017669B1 (fr) Procede de production d'alpha, omega-aminonitriles aliphatiques
EP1060158B1 (fr) Procede de production de diamines alpha, omega aliphatiques
DE19636767A1 (de) Verfahren zur Herstellung von aliphatischen alpha, omega-Aminonitrilen
DE19646436A1 (de) Verfahren zur Herstellung von aliphatischen, alpha,omega-Aminonitrilen
DE19754571A1 (de) Verfahren zur Herstellung von variablen Gemischen aus Cyclohexylamin und Dicyclohexylamin

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 97199516.8

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AU AZ BG BR BY CA CN CZ GE HU IL JP KG KR KZ LT LV MD MX NO NZ PL RO RU SG SI SK TJ TM TR UA US AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1997941948

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: PA/a/1999/002141

Country of ref document: MX

ENP Entry into the national phase

Ref document number: 1998 513186

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2265488

Country of ref document: CA

Ref document number: 2265488

Country of ref document: CA

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1019997001940

Country of ref document: KR

Ref document number: PV1999-810

Country of ref document: CZ

WWE Wipo information: entry into national phase

Ref document number: 09254454

Country of ref document: US

Ref document number: 1999/00516

Country of ref document: TR

WWP Wipo information: published in national office

Ref document number: PV1999-810

Country of ref document: CZ

WWP Wipo information: published in national office

Ref document number: 1997941948

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1019997001940

Country of ref document: KR

WWR Wipo information: refused in national office

Ref document number: PV1999-810

Country of ref document: CZ

WWG Wipo information: grant in national office

Ref document number: 1997941948

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 1019997001940

Country of ref document: KR